Diazo amino-containing pulverulent dyeing preparations showing reduced dust formation



3453 066 DIAZO 'AMINO-CONTAINING PULVERULENT DYEING PREPARATIONS SHOWING RE- DUCED DUST FORMATION- Hasso Hertel, Offenbach (Main), Germany, assignor to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning, Frankfurt am Main, Germany, a corporation of Germany N Drawing. Filed June 28, 1965, Ser. No. 467,676 Claims priority, application Grmany,'June 30, 1964,

Int. Cl. D061), 1/02, 3/04 US. Cl. s-4s 2 Clainis ABSTRACT OF THE DISCLOSURE Pulverulent dyeing preparations substantiallyfree from dusting comprising (1) a diazoamino compound formed by coupling diazotized aromatic amines with cyanamide or alkali and alkaline earth metal salts thereof (2) an aliphatichydrocarbon and (3) an alkylsulfonamido-alkyl carboxylic acid salt surface active agent.

It is known that by coupling diazotized aromatic weight and further condensed with a halogen-carboxylic acid. By 'thismethod, high-molecular alkylsulfonamido carboxylic acids are obtained which still'contain a rather large portion of unmodified hydrocarbons as well as sulfonamides and'which are converted in known manner into the corresponding alkali-metal or alkaline earth metal salts.

If as dust preventing agent a mixture of alkylsulfonarnido-alkyl-carboxylic acid salts and hydrocarbon is used, both components are generally applied in a ratio of 2:1

. to 1:2 (by weight). When using the components in the aforementioned relationship, the powders poor in dust, when used later on in the dyeing of textiles, will not give rise to the separation of hydrocarbons.

In order to arrive with a certain amount of dust-preventing substance at a maximum of activity, it is necessary to contact the dust-reducing agent as intimate-1y as amines with cyanamide or its alkali'metal or alkaline" earth metal salts, water-soluble diazo-amino compounds are obtained which are suitable for preparing waterinsoluble azo-dyestuffs on vegetable fibers. Said diazoamino compounds being used in the form of powders,

strongly tend to form dust which unfavorably influences the possibilities of application. Since it causes coughing and sneezing as well as swelling of the mucous membranes of the na-sopharynx, this dust is very disagreeable for the human organism. Due to this reason, the compounds in questio'nwere not used up to now in industrial practice.

Now I have found that dyeing powders showing reduced dust-formation and containing a diazo-amino compound corresponding to the general formula (I) R-N=NN-'CN wherein R represents an aromatic radical and Me is a monovalent radical of an alkali metal or an alkaline earth metal are obtained by intimately mixing the diazo-amino compound with an aliphatic hydrocarbon or a mixture of aliphatic hydrocarbons having preferably 8 to 18 carbon atoms and a surface-active agent of the general formula wherein R represents hydrogen or a low-molecular alkyl group preferably containing 1-4 carbon atoms, R represents an alkyl group with 8 to 18 carbon atoms, R stands for a straight-chained or branched bivalent alkylene group, preferably containing 12 carbon atoms and Me stands for an alkali or alkaline earth metal radical.

The diazo-amino compounds "can likewise be mixed directly with a mixture of said hydrocarbons and alkylsulfonamide-alkyl-carboxylic acid salts which are obtained as follows: Fractions of high-molecular aliphatic hydrocarbons of a boiling range between about 150 and 350 C. are simultaneously reacted with sulfur dioxide and chlorine according to usual methods of sulfochlorination (cf., for instance, B. F. Aisinger 'Berichte *der Deutschen Chemischen Gesel-lschaft,?.7.7. (1944), pages 191-194).

When operating according to said method, it is of advantage to subject to sulfo-chlorination only one half of the hydrocarbons. The sulfochlorination mixture is reacted with ammonia or a primary alkylamine of low molecular device.

.pound and then grinding themixture in a suitable mill, for instance in a mill provided with agitator,beater or stud. Another grinding method consists in continuously.

.introducing the dust-reducing agent during the grinding. operation into the mill or into the preliminary breaking The amount of dust-reducing agent not badly influencing the fastness to;sto ring of the goods depends on the composition of the dust-reducing agent and the type of; the diazo-amino compound; in general amounts of about 2.5 to about 20 percent by weight, calculated on the weight of the diazoam'ino compound will be used. If, for instance, a mixture of about equal parts of aliphatic hydrocarbon and surface-active agent is applied, there are. favorably used about 7 to 15 percent by weight of'the mixture, calculated on a diazo-amine compound. In practice, however, dyeing preparations. will generally be used, which for technical reasons, for instance in 'order to improve the penetration of the dye .or the fastness to rubbing, or in their property as wetting agent, in addition to the diazo-amino compound still contain further additions such as inorganic compounds, 'for instance, alkali metal chlorides, alkali metal sulfates, alkali metal carbonates or alkali metal phosphates and/ or orgnic compounds such as alkai metal salts of ethylenediaminotetracetic acid, condensation products from aminoalkylsulfonic acids and high-molecular fatty acids,

' dialkyl-naphthalene-sulfonic acids or condensation productsfrom formaldehyde with naphthalene-sulfonic acids. Generally, dyeing preparations of said kind contain about 30 to 70% of diazoamino compound. If, forreducing the dust formation, a mixture of about equal parts of aliphatic hydrocarbon and surface-active substance is used,

. about 1 to 15 percent by weight, preferably 4 to 7 percent by weight, of dust-reducing agent will be required.

The efficiency of the dust-reducing agent is suitably examined by means of the photo-electric method. For this purpose, a sample of the substance is dropped through a vertical tube int-o a measuring box, wherein in lateral position to the tube, a lamp is arranged, and opposite thereto, a photo-cell. The reduction in the intensity of light caused by the formation of ,dust is suitably read off on the galvanometer gauged to a standard percentage of transparency.

As diazo-amino compounds of the general Formula I which can be prevented from dusting according to the process of the present invention, there enter into consideration, for instance, compounds obtainedby coupling diazotized primary aromatic amines with cyanamide or its alkali metal salts according to the process disclosed in German patent specification 614,198. Preferably, diazoamino compounds of the Formula I are used in which R represents a phenyl group, which may be substituted by one or several halogen atoms, phenoxy groups, trifluoromethyl groups, nitro groups or low-molecular alkyl-, alkoxyor alkylsulfone groups.

As aliphatic hydrocarbons with 8 to 18 carbon atoms there can be used, for instance, octane, decane, dodecane or octadecane or mixtures of aliphatic hydrocarbons such as they are obtained, for instance, by the Fischer- Tropsch synthesis (boiling range between about 150 and 350 C.). Preferably a mixture of aliphatic hydrocarbons containing 12-18 carbon atoms is used.

As surface-active agents of the Formula II there are used the reaction products of alkylsulfochlorides or of mixtures of alkylsulfochlorides, with aliphatic aminocarboxylic acids or the reaction products of alkylsulfonamides or of mixtures of alkylsulfonamides with aliphatic -halogen-carboxylic acids, as they are obtained, for instance, according to German patent specification 767,071. Especially suitable is the sodium salt of alkylsulfonamidoacetic acid (with 12-18 carbon atoms in the alkyl group) obtained by reaction of an alkylsulfonamide based on a mixture of hydrocarbons containing about 12 to 18 carbon atoms.

The following examples serve to illustrate the present Example 1 In a mixer provided with plough blade, of a capacity of 5 liters, 944 grams of a diazo-amino compound of 68% strength from diazotized 1-amino-2,5-dichlorobenzene and sodium cyanamide, 127 grams of a condensation product (A) from oleic acid chloride and N-methyltaurine and 544 grams of anhydrous sodium sulfate are mixed. 92 grams of a mixture (B) consisting of about equal parts of a mixture of aliphatic hydrocarbons, preferably of straight chain, with 12-18 carbon atoms (mepasine) and a sodium salt of an alkylsulfonamido-acetic acid (the alkyl radical having 12 to 18 carbon atoms) are simultaneously added. After having been mixed, the substance is ground in a Condux cross-beater mill without screening device. A dyeing preparation is obtained which shows a formation of dust of only one thirtieth 1 of that shown by an untreated diazoamino compound preparation.

The composition of other dyeing preparations poor in dust, obtainable according to the present invention and figures illustrating said reduction are to be seen from the following table. (The figures represent parts by Weight invention but they are not intended to limit it thereto: 25 or percent by weight.)

Condensation Mixture of dust Diazoamino compound of Net content Amount (parts product A (parts reducing agents Sodium sulfate Reduction of dust the formula (percent) by weight) by welght) (parts by Weight) (parts by weight) i t;

N=NNCN 39 720 46 30. 5 94 90 (I) CH3 N=NN-CN 1, 275 99 59. 5 217 5 --N=N--N-ON 70. 3 1, 270 104 52 224 30 l ON:N-NCN 42. 1 880 S5 57 128 7 (I) CH N=Nl lICN 86 S00 57 22 262 CzHs S Oz-N i =N-N-CN G0 19 85 Example 2 When operating according to the method described in Example 1, but using 1210 grams of a diazoamino compound of 71.5% strength from diazotized 1-amino-2- methyl-S-nitrobenzene and sodium cyanamide, 201 grams of the condensation product A mentioned in Example 1 and 251.5 grams of anhydrous sodium sulfate as well as 87.5 grams of the mixture of dust reducing agents B (cf. Example 1) a dyeing preparation is obtained which shows a formation of dust of only one fortieth 4 of that shown by an untreated preparation.

In a similar manner the diazo-amino compounds from diazotized 1-amino-2-methoxy 4 nitrobenzene or 1- amino 2 methyl 5 chlorobenzene, 1 amino 2- methyl 4 nitrobenzene or 1 amino 2 methyl 4- chlorobenzene and sodium cyanamide can be converted into a product poor in dust.

By applying the same method of operation suitable dyeing preparations of the following compositions will be obtained:

(1) 800 parts by weight of a diazo-amino compound of 86% strength of the formula 22 parts by weight of the dust reducing mixture B described in Example 1, 262 parts by weight of sodium sulfate, 57 parts by weight of a condensation product from formaldehyde and naphthalene-Z-sulfonic acid.

The formation of dust is reduced by 90% v (2) 470 parts by weight of a diazo-amino compound of 76% strength of the formula 31 parts by weight of the dust reducing mixture B described in Example 1, 16 parts by weight of a mixture of aliphatic hydrocarbons with 12-18 carbon atoms (rnepasine), 94 parts by weight of the sodium salt of 2,5-dibutyla-naphthalene-sulfonic acid.

The formation of dust is reduced by 90%.

(3) 560 parts by weight of a diazoamino compound of 50% strength corresponding to the formula C Ha I Cal2 56 parts by weight of the dust-reducing mixture B described in Example 1, 112 parts by weight of the sodium salt of 2,5-dibutyl-a-naphthalenesulfonic acid.

The formation of dust is reduced by 87%.

I claim:

1. A pulver-ulent dyeing preparation having reduced dust formation consisting essentially of (1) a diazoamino compound of the formula wherein R is phenyl or substituted phenyl, said substituents being selected from the group consisting of chlorine, phenoxy, trifiuoromethyl, nitro, lower alkyl, lower alkoxy, sulfonic acid di-(lower alkyl)- amide and lower alkylsulfone, the substituted phenyl containing at least one of said substituents, and Me represents a monovalent radical of alkali or alkaline earth metal,

(2) at least one saturated aliphatic hydrocarbon having 8 to 18 carbon atoms and (3) a surface active agent of the formula wherein R stands for hydrogen or lower alkyl, R stands for an alkyl group having 8 to 18 carbon atoms, R stands for alkylene having one or two carbon atoms and Me stands for an alkali or alkaline earth metal radical, components 2 and 3 being present in a weight ratio of 2:1 to 1:2 and in a total amount of between 2.5 to 20% based on the weight of diazoamino compound employed.

2. The preparation of claim 1 wherein components 2 and 3 are present in a total amount of between 7' to 15% based on the weight of diazoamino compound employed.

References Cited UNITED STATES PATENTS 2,054,397 9/1936 Taube 845 3,294,477 12/ 1966 Tamer et al.

FOREIGN PATENTS 587,544 11/1959 Canada. 693,765 7/ 1953 Great Britain.

FLOYD D. HIGEL, Primary Examiner.

US. Cl. X.R. 

